CN106636668B - A kind of waste and old electromagnetic wire copper refining agent and its preparation method and application - Google Patents
A kind of waste and old electromagnetic wire copper refining agent and its preparation method and application Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0026—Pyrometallurgy
- C22B15/006—Pyrometallurgy working up of molten copper, e.g. refining
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/001—Dry processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/10—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals with refining or fluxing agents; Use of materials therefor, e.g. slagging or scorifying agents
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Abstract
The present invention relates to a kind of waste and old electromagnetic wire copper refining agent and its preparation method and application.The refining agent can have preferably by percentage to the quality are as follows: V=1.0-5.0%；Sr=1.0-5.0%, B=0.5~2.5%；Mg=5.5~7.5%；Y=5~10%, Ce=5~10% remaining are Cu.Preparation method are as follows: by Cu-B-Y-Ce-Mg intermediate alloy, Cu-Sr intermediate alloy is broken into respectively under partial size to be covered to obtain the refining agent with high-purity oxygen-free copper suitcase by setting ratio after mixing in the vanadium of 10mm fragment and partial size less than 10mm.The refining agent can be used for waste and old copper magnet wire refining oxygen-free copper, and additional amount is 1.0 ‰~the 6.5 ‰ of melt quality.Refining agent deoxidation, desulfurization, dealuminzation, deferrization, nickel removal and other effects designed by the present invention are good, do not generate secondary pollution to copper liquid.Composition design of the present invention is reasonable, and preparation process is simple, is convenient for large-scale industrialization application.
Description
Technical field
The present invention relates to a kind of copper refining agent and its preparation method and application, belong to metallurgical industry recycled copper liquid refining agent and open
Send out technical field.
Background technique
Countries in the world today focuses on environmental protection and sustainable development very much, and the regeneration of resource is researched and developed as various countries
Emphasis.The cable industry of Europe and Japan attaches great importance to resource regeneration, as Hitachi, Japan cable companies are persistently dedicated to
Develop the recovery and utilization technology of waste electric wire cable.High-end electrician's oxygen-free copper bar is directly manufactured with waste and old electromagnetic wire copper, it will section
It saves a large amount of resource and reduces environmental pollution, key is must to break through high purification melt preparation key technology, to ensure copper
Amount >=99.95%, oxygen content≤10ppm.Its technical difficulty is mainly manifested in the control of oxygen content and impurity content.It is dissolved in copper
Impurity can all reduce the conductivity of copper, non-solid solution impurity and copper form meltable eutectic and frangible compounds, acutely reduce copper
Plasticity, influence the processing performance and mechanical property of copper.Waste and old electromagnetic wire copper generally uses low oxygen glitter copper lever to prepare, oxygen content
Generally 30ppm-250ppm.Electromagnetism product waste and old for low middle-end, such as three-level bar, Fe, S, Se, Te, Bi, Pb equal size are also past
It is past higher, high-end electrician's oxygen-free copper bar is directly such as made using waste and old electromagnetic wire copper, needs to carry out depth to waste and old electromagnetic wire copper
Then oxidation removes the various impurity in recycled copper by slag making, this requires restoring to copper liquid, restore excessive, copper liquid
Interior oxygen content drops too low, and hydrogen content can increase sharply, and hydrogen embrittlement problem, slab easy fracture occurs.Therefore, to waste and old electromagnetic wire
Copper directly manufactures electrician's copper bar of standby high-quality out, obtains the copper melts of high purification, it is necessary to develop effective refining agent.
Copper melts method of deoxidation mainly has: 1) using phosphorus deoxidation；2) lithium deoxidation is used；3) magnesium deoxidation is used；4) boron deoxidation is used；5) it uses
CaB6Deoxidation etc..There is different degrees of deficiency in above method.Phosphorus is cheap deoxidier, but the residual of a small amount of phosphorus will be shown
Write the electrical and thermal conductivity for reducing copper；Lithium is a kind of strong oxidizer, but its chemical property and its active, is not easy to store, and add tired
It is difficult；Magnesium easily leads to inclusion defect；The effect of boron deoxidation is not so good as magnesium and lithium；CaB6Although deoxidation effect is good, its preparation process
In recovery rate it is low, price is high.Method or refining agent described above can only remove the oxygen element in copper removal, for other in copper
Impurity element can not effectively remove.
In copper and copper alloy, rare earth can play the role of degasification and remove slag, and purify melt.It is added in copper and copper alloy
Rare earth element effectively can deaerate and remove impurity by the interaction of rare earth and impurity element, improve or improve alloy
Various performances.1. deoxidation: the oxide that rare earth is generated with oxygen easily enters slag phase and is removed；2. desulfurization: the principle phase with deoxidation
Seemingly；3. dehydrogenation: rare earth can react the low-density hydride for generating REH type with the hydrogen in copper liquid, easily float up to copper liquid surface, enter
Slag phase and be removed；
Using rare earth as the patent of copper refining agent, has relevant report, such as: a kind of patent [200910043041.8] " essence
Refine the high rare-earth content intermediate alloy refining agent and preparation method thereof of copper scap " in, it was recently reported that its refining agent rare earth developed
Element includes lanthanum, cerium, yttrium, praseodymium etc., which can effectively remove the impurity such as Zn, Fe, Pb, O, S, P in copper scap, the essence
Refine the similarly suitable recycled copper of agent refining, but in the patent for the concrete content of yttrium, praseodymium and its in refining process
Specific effect is not described, and the refining agent for Ni removal almost without effect, in addition to this, rare earth element consumption
It is too big, cause cost high.Described in patent [CN1133347A] " refining agent for molten copper and preparation method " it is a kind of containing B,
The refining agent of Mg and rare earth can effectively remove hydrogen, oxygen and sulphur in copper, the equally applicable recycled copper of the refining agent, but this is specially
What specific rare earth constituent element is in benefit, is not described.How much above-mentioned patent is minimum to the final oxygen content for obtaining product is being worth
Do not have explicitly stated, and there is also some problems for removing of the refining agent to other impurity elements.
In conclusion how to further increase the deoxidation of copper, desulfurization and the refining agent skill for removing other impurities element in copper removal
Art directly prepares high-quality electrician's oxygen-free copper bar using waste and old electromagnetic wire copper to realize, meets high sophisticated technology field pair
Highly conductive, high heat-conducting copper alloy product quality requirement has become a top priority.
Summary of the invention
The present invention provides a kind of waste and old copper magnet wire production high-quality for shortcoming existing for existing copper refining agent
The refining agent of oxygen-free copper bar and its preparation.
A kind of copper refining agent of the present invention；It is calculated in mass percent including following components:
V0.5-10.0%, preferably 1.0-5.0%, further preferably 1.5-3.0%；
Sr 0.5-10.0%, preferably 1.0-5.0%, further preferably 1.5-3.0%；
B 0.5-5%, preferably 0.5~2.5%, further preferably 0.5-1.5%；
Mg 5.5~7.5%, preferably 6.0-7.0%；
Y 4~12%, preferably 5~10%, further preferably 6.5-7.5%；
Ce 4~12%, preferably 5~10%, further preferably 6.5-7.5%；
Surplus is copper.
Preferably, a kind of copper refining agent of the present invention；It counts in mass ratio, V:Sr=1:1-1.2:1.
Preferably, a kind of copper refining agent of the present invention；It counts in mass ratio, Y:Ce=0.8:1-1.2:1.
A kind of copper refining agent of the present invention；The refining agent by Cu-V intermediate alloy and/or vanadium metal, Cu-Sr intermediate alloy,
Cu-B-Y-Ce-Mg alloy and oxygen-free copper composition.
Preferably, a kind of copper refining agent of the present invention；The vanadium metal, Cu-Sr intermediate alloy, Cu-B-Y-Ce-Mg
Alloy after mixing, is coated in copper sheet made of anaerobic fine copper.
A kind of copper refining agent of the present invention；It is described
The Cu-Sr intermediate alloy, chemical component are as follows: Sr=20-40wt%, remainder are Cu；
The Cu-B-Y-Ce-Mg alloy, chemical component are as follows: B=0.5~2.5wt%, Mg=5.5~7.5wt%, Y
=5~10wt%, Ce=5~10wt%, remainder are Cu, and remainder is Cu.
A kind of preparation method of copper refining agent of the present invention: by Cu-B-Y-Ce-Mg intermediate alloy, Cu-Sr intermediate alloy difference
It is broken under partial size and uses high-purity oxygen-free copper suitcase after mixing by setting ratio in the vanadium of 10mm fragment and partial size less than 10mm
It covers；Obtain the refining agent.
A kind of preparation method of copper refining agent of the present invention: the Cu-B-Y-Ce-Mg alloy is prepared by following step
:
Step 1
Cathode copper by purity more than or equal to 99.995% is placed in the dry pot of graphite of vacuum melting furnace, is evacuated to
10-3It is initially powered up melting after Pa, is vacuumized in heating, until cathode copper melts, obtains copper liquid；
Step 2
Stopping vacuumizes, and is passed through the high purity inert gas that purity is more than or equal to 99.999%, and control furnace pressure is 0.5
~1 atmospheric pressure reduces melt temperature to 1150~1230 DEG C, A, B, C is added in copper liquid by design proportion, are warming up to
1200-1250 DEG C, when A, B, C melt, cooling obtains Cu-B-Y-Ce-Mg alloy；The A is the Mg block that surface is coated with copper foil
The Cu-B alloy block of copper foil is coated with surface；The B is the Y block of Cu-Y intermediate alloy or surface cladding copper foil, and C is Cu-
The Ce block of Ce intermediate alloy or surface cladding copper foil.
A kind of preparation method of copper refining agent of the present invention: the lumpiness of the Mg block is less than 20mm, and purity is more than or equal to
99.99%.
A kind of preparation method of copper refining agent of the present invention: the lumpiness of the Cu-B alloy block is less than 20mm.As preferred institute
It states in Cu-B alloy block, the mass percentage of B is 4-8%.
A kind of preparation method of copper refining agent of the present invention: the Y block, Ce block lumpiness be respectively less than 20mm.Preferably, institute
State Y block, the purity of Ce block is all larger than equal to 99.99%.
A, B, C are added in copper liquid scheme as a further preference, are warming up to 1200-1250 DEG C, when A, B, C are molten
Change, is cooled to 1150~1200 DEG C, then pours into water cooling swage and obtain Cu-B-Y-Ce-Mg alloy.
A kind of preparation method of copper refining agent of the present invention: the Cu-Sr intermediate alloy is prepared by following step:
Step I
Cathode copper by purity more than or equal to 99.995% is placed in the dry pot of graphite of vacuum melting furnace, is evacuated to
10-3It is initially powered up melting after Pa, is vacuumized in heating, until cathode copper melts, obtains copper liquid；
Step II
Stopping vacuumizes, and is passed through the high purity inert gas that purity is more than or equal to 99.999%, and control furnace pressure is 0.5
~1 atmospheric pressure reduces melt temperature to 1150~1200 DEG C, D is added in copper liquid, Cu-Sr intermediate alloy is obtained；It is described
D is the Sr block that surface is coated with copper foil.
A kind of preparation method of copper refining agent of the present invention: in step II, the lumpiness of the Sr block is less than 20mm, and purity is big
In equal to 99.99%.
Inert gas of the present invention is selected from least one of helium, argon gas, neon, preferably argon gas.
A kind of application of copper refining agent of the present invention, including the refining agent is used for waste and old copper magnet wire and refines oxygen-free copper.
A kind of application of the refining agent with waste and old electromagnetic wire copper production high-quality oxygen-free copper bar of the present invention, the application are as follows:
The refining agent is used for the technique that waste and old copper magnet wire produces oxygen-free copper bar by initial refining.
A kind of application of the refining agent with waste and old electromagnetic wire copper production high-quality oxygen-free copper bar of the present invention, the refining agent are pressed
It is refined in the 1.0 ‰ of melt quality~6.5 ‰ addition melts.The melt is gained liquid after the fusing of waste and old electromagnetic wire copper
Body.
The advantages and positive effects of the present invention
1. using waste and old electromagnetic wire copper refining agent of the invention, in refining process, additional amount is only melt quality
1.0 ‰~6.5 ‰, it can be obtained good refining effect, significantly reduce cost.
2. directly manufacturing oxygen-free copper material with waste and old electromagnetic wire copper copper, technical difficulty essentially consists in oxygen content and impurity content
Control, generally all can be controlled in 10ppm with electrolysis copper bar oxygen content and hereinafter, but with waste and old electromagnetic wire copper copper bar directly processed
Reach These parameters, then needs to carry out deep oxidation to copper scap, this also increases the recovery time of copper liquid, restored
Head, oxygen content drops too low in copper liquid, and hydrogen content can increase sharply, and hydrogen embrittlement problem, slab easy fracture occur.What is be dissolved in copper is miscellaneous
Matter can all reduce the conductivity of copper, reduce quantity, person's character and metallurgy condition that degree depends on impurity, another part non-solid solution
Impurity (O, S, Bi, Pb) on the conductivity for reducing copper although influencing smaller but forming meltable eutectic and brittleness chemical combination with copper
Object acutely reduces the plasticity of copper, influences the cold and hot working performance of copper.The collaboration that the present invention passes through suitable B, Mg, V, Ce, Y, Sr
Effect, has achieved the effect that unexpected, is in particular in, the present invention can efficient deoxidation, moreover it is possible to efficient removal S, Bi, Pb,
Ni, Fe, Al, especially its effect is especially prominent in terms of removing Ni, Fe, Al.
3. leading to refining agent of the present invention alloying element in smelting process since the present invention devises special processing mode
Burn out rate lower than 1.6%, minimum even up to 0.5%.And then guarantee the stability of refining agent component set by the present invention.
In short, the present invention utilizes the synergistic effect of B, Mg, V, Ce, Y, Sr, unexpected effect is obtained, especially with phase
Inexpensive light rare earth elements and other elements is combined to remove Ni, Fe, Al, O in waste and old copper magnet wire etc. inexpensive vanadium miscellaneous
This effect of matter, will promote waste and old copper magnet wire to recycle industry.Refining agent designed by the present invention is also avoided that copper simultaneously
The secondary pollution of melt.
Specific embodiment
Refining agent used in embodiment is grouped as following groups under having by percentage to the quality:
B:1.0%；Y:7.0%；Ce:7.0%；Mg:4.8%；Sr:3.0%；V:3.0%；Surplus is copper.
Refining agent is by Cu-1.2B-8Y-8Ce-7.5Mg (wt%) intermediate alloy block, Cu-30Sr (wt%) intermediate alloy, gold
Belong to V particle composition；Wherein the partial size of each intermediate alloy block, metal V particle is less than 10mm.Cu-1.2B-8Y-8Ce-7.5Mg
(wt%) intermediate alloy block, Cu-30Sr (wt%) intermediate alloy, metal V particles coat are in anaerobic copper sheet.
The Cu-B-Y-Ce-Mg alloy is prepared by following step:
Step 1
Cathode copper by purity more than or equal to 99.995% is placed in the dry pot of graphite of vacuum melting furnace, is evacuated to
10-3It is initially powered up melting after Pa, is vacuumized in heating, until cathode copper melts, obtains copper liquid；
Step 2
Stopping vacuumizes, and is passed through the high purity inert gas that purity is more than or equal to 99.999%, and control furnace pressure is 0.5
~1 atmospheric pressure reduces melt temperature to 1150~1230 DEG C, A, B, C is added in copper liquid by design proportion, are warming up to
1200-1250 DEG C, when A, B, C fusing, 1150~1200 DEG C is cooled to, then pours into water cooling swage and obtains Cu-B-Y-Ce-Mg
Alloy.；The A is that surface is coated with the Mg block of copper foil and surface is coated with the Cu-B alloy block of copper foil；The B is among Cu-Y
The Y block of alloy or surface cladding copper foil, C are the Ce blocks of Cu-Ce intermediate alloy or surface cladding copper foil.
The lumpiness of the Mg block is less than 20mm, and purity is more than or equal to 99.99%.
The lumpiness of the Cu-B alloy block is less than 20mm.As in the preferred Cu-B alloy block, the mass percentage of B
For 4-8%.
The Y block, Ce block lumpiness be respectively less than 20mm.Preferably, the purity of the Y block, Ce block is all larger than and is equal to
99.99%.
The Cu-Sr intermediate alloy is prepared by following step:
Step I
Cathode copper by purity more than or equal to 99.995% is placed in the dry pot of graphite of vacuum melting furnace, is evacuated to
10-3It is initially powered up melting after Pa, is vacuumized in heating, until cathode copper melts, obtains copper liquid；
Step II
Stopping vacuumizes, and is passed through the high purity inert gas that purity is more than or equal to 99.999%, and control furnace pressure is 0.5
~1 atmospheric pressure reduces melt temperature to 1150~1200 DEG C, D is added in copper liquid, Cu-Sr intermediate alloy is obtained；It is described
D is the Sr block that surface is coated with copper foil.
The lumpiness of the Sr block is less than 20mm, and purity is more than or equal to 99.99%.
Embodiment 1
Taking surface treated copper content is that the electromagnetic wire 50kg of 99.72wt% carries out refining treatment to it.It first will be electric
Magnet-wire is 2 hours dry at 350 DEG C, is then placed in fusing in intermediate frequency furnace, and temperature is 1160 DEG C -1190 DEG C, is forged with by 700 DEG C
The calcining charcoal of burning covers copper liquid, this refining agent 0.15kg is added, is slightly stirred with 700 DEG C of burnt graphite rods, uses slag making
Agent slag making casts in cylindrical swage after scarfing cinder, obtains ingot casting, is turned surface defect.Chemical analysis copper content is
99.96wt%, resistivity are 0.01720 × 10-6Ω m, oxygen content 8ppm.
Embodiment 2
The chemical component of useless electromagnetic wire is as shown in table 1, and the waste and old copper pipe 100kg of the ingredient is taken carry out at refining to it
Reason.It is first that copper scrap pipe is 2 hours dry at 500 DEG C, it is then placed in fusing in intermediate frequency furnace, temperature is 1180 DEG C -1210 DEG C, is used
The graphite powder calcined by 700 DEG C covers copper liquid, this refining agent 0.4kg is added, is slightly stirred with 700 DEG C of burnt graphite rods
It mixes, casting obtains ingot casting with swage after scarfing cinder, and chemical component is as shown in table 1, it is apparent that, which, which removes, has
Effect reduces outside other impurities, also can effectively reduce the content of impurity F e, Ni.
Table 1
| Before refining (wt%) | After refining (wt%) | |
| O | 0.0150 | 0.0090 |
| Al | 0.0100 | 0.0070 |
| Bi | 0.0060 | 0.0001 |
| Cr | 0.0031 | 0.0009 |
| Fe | 0.0096 | 0.0011 |
| Mn | 0.0080 | 0.0006 |
| Ni | 0.0100 | 0.0007 |
| Pb | 0.0150 | 0.0065 |
| Si | 0.0160 | 0.0092 |
| Sb | 0.0012 | 0.0003 |
| Sn | 0.0080 | 0.001 |
| P | 0.0100 | 0.002 |
| It is total | 0.0384 |
Embodiment 3
Taking surface treated copper content is that the waste and old electromagnetic wire copper copper 100kg of 99.40wt% refine to it
Processing.It is first that it is 2 hours dry at 350 DEG C, it is then placed in fusing in intermediate frequency furnace, temperature is 1160 DEG C -1190 DEG C, with warp
700 DEG C of burnt charcoal covering copper liquids are crossed, this refining agent 0.5kg are added, the graphite rod calcined with 700 DEG C slightly stirs, and adds
Enter slag former, cast in after scarfing cinder in cylindrical swage, obtain ingot casting, is turned surface defect, cold forging is extremelyAnnealing
1 hour, cold drawing was processed intoWire rod, chemical analysis copper content be 99.95wt%, resistivity be 0.01721 × 10-6Ω m,
Oxygen content is 8ppm.Mechanical performance is Rm=412MPa.
Embodiment 4
[O] content before waste and old electromagnetic wire copper copper refining are as follows: 0.0120%；[S]: 0.0032%.Take above-mentioned waste and old copper electromagnetism
Line 100kg carries out carrying out refining treatment to it.It is first that it is 2 hours dry at 500 DEG C, it is then placed in fusing in intermediate frequency furnace,
Temperature is 1130 DEG C -1150 DEG C, covers copper liquid with by 700 DEG C of burnt graphite powders, this refining agent 0.3kg is added, with warp
700 DEG C of burnt graphite rods are crossed slightly to stir, after scarfing cinder casting with swage in, obtain ingot casting, on analyzer detect hydrogen,
Oxygen, sulfur content, [O]: 0.0009%；[S]: 0.0008%.
If there is comparative example, comparative example please be fill into.Comparative example can greatly increase authorization probability of the invention.
Comparative example 1
The other components of refining agent are completely the same with embodiment 2, only lack V, by the refining agent of comparative example 1 according to implementation
The application method of example, processing is with a batch of waste and old copper pipe, and each uniform embodiment 1 of conditional parameter is consistent when processing, as a result,
Chemical analysis copper content is 99.72wt%, and resistivity is 0.01730 × 10-6Ω m, oxygen content 110ppm.
Comparative example 2
The other components of refining agent are completely the same with embodiment 2, only lack V, Sr, by the refining agent of comparative example 2 according to
The application method of embodiment 1, processing is with a batch of waste and old copper pipe, and each uniform embodiment 1 of conditional parameter is consistent when processing, knot
Fruit is that its ability for removing the impurity such as Ni, Fe, Als declines to a great extent compared to refining agent of the present invention as shown in table 2.
Table 2
| Before refining (wt%) | After refining (wt%) | |
| O | 0.0150 | 0.0120 |
| Al | 0.0100 | 0.0080 |
| Bi | 0.0060 | 0.0060 |
| Cr | 0.0031 | 0.0009 |
| Fe | 0.0096 | 0.0053 |
| Mn | 0.0080 | 0.0006 |
| Ni | 0.0100 | 0.0084 |
| Pb | 0.0150 | 0.0040 |
| Si | 0.0160 | 0.0107 |
| Sb | 0.0012 | 0.0003 |
| Sn | 0.0080 | 0.0024 |
| P | 0.0100 | 0.0042 |
| It is total | 0.0384 |
Comparative example 3
The intermediate alloy component of refining agent is completely the same with embodiment 3, by among Cu-1.2B-8Y-8Ce-7.5Mg,
Cu-30Sr intermediate alloy, metal V particle 100:14:1 ratio in mass ratio mix.Resulting refining agent other components with reality
It is consistent to apply example 3, but the mass ratio of V and Sr is 1:4.6.By the refining agent of comparative example 3 according to the application method of embodiment 3, processing
With a batch of waste and old copper magnet wire, when processing the uniform embodiment 3 of each conditional parameter it is consistent, as a result, chemical analysis copper contains
Amount is 99.79wt%, and resistivity is 0.01728 × 10-6Ω m, oxygen content 14ppm, mechanical performance Rm=396MPa are low
In the use resulting alloy property of refining agent of the present invention.It can be seen that the mass ratio of control V and Sr is also most important.
By embodiment and comparative example as can be seen that the synergistic effect energy between designed appropriate each component through the invention
Reaching can efficient deoxidation, moreover it is possible to efficient removal S, Bi, Pb, Ni, Fe, Al, the especially purpose of efficient removal Ni, Fe, Al.
Claims (10)
1. a kind of copper refining agent；It is characterized by: being calculated in mass percent including following components:
V0.5-10.0%；
Sr 0.5-10.0%；
B 0.5-5%；
Mg 5.5~7.5%；
Y 4~12%；
Ce 4~12%；
Surplus is copper；
In the copper refining agent, count in mass ratio, V:Sr=1:1-1.2:1.
2. a kind of copper refining agent according to claim 1；It is characterized by: the refining agent by vanadium metal, Cu-Sr among
Alloy, Cu-B-Y-Ce-Mg alloy and oxygen-free copper composition.
3. a kind of copper refining agent according to claim 1；It is characterized by: vanadium metal, Cu-Sr intermediate alloy, Cu-B-Y-
Ce-Mg alloy after mixing, is coated in copper sheet made of anaerobic fine copper.
4. a kind of copper refining agent according to claim 2；It is characterized by:
The Cu-Sr intermediate alloy, chemical component are as follows: Sr=20-25wt%, remainder are Cu；
The Cu-B-Y-Ce-Mg alloy, chemical component are as follows: B=0.5~2.5wt%, Mg=5.5~7.5wt%, Y=5~
10wt%, Ce=5~10wt%, remainder are Cu.
5. a kind of method for preparing the copper refining agent as described in claim 1-4 any one；It is characterized by: by Cu-B-Y-Ce-
Mg intermediate alloy, Cu-Sr intermediate alloy are broken into vanadium of the partial size less than 10mm fragment and partial size less than 10mm by setting ratio respectively
Example is covered with high-purity oxygen-free copper suitcase after mixing；Obtain the refining agent.
6. a kind of preparation method of copper refining agent according to claim 5；It is characterized in that the Cu-B-Y-Ce-Mg is closed
Gold is prepared by following step:
Step 1
Cathode copper by purity more than or equal to 99.995% is placed in the dry pot of graphite of vacuum melting furnace, is evacuated to 10-3After Pa
It is initially powered up melting, is vacuumized in heating, until cathode copper melts, obtains copper liquid；
Step 2
Stopping vacuumizes, and is passed through the high purity inert gas that purity is more than or equal to 99.999%, and control furnace pressure is 0.5~1
Atmospheric pressure reduces melt temperature to 1150~1230 DEG C, A, B, C is added in copper liquid by design proportion, are warming up to 1200-1250
DEG C, when A, B, C melt, cooling obtains Cu-B-Y- Ce-Mg alloy；The A is the Mg block and surface packet that surface is coated with copper foil
It is covered with the Cu-B alloy block of copper foil；The B is the Y block of Cu-Y intermediate alloy or surface cladding copper foil, and C is closed among Cu-Ce
The Ce block of gold or surface cladding copper foil.
7. a kind of preparation method of copper refining agent according to claim 6；It is characterized by:
The lumpiness of the Mg block is less than 20mm, and purity is more than or equal to 99.99%；
The lumpiness of the Cu-B alloy block is less than 20mm；
The Y block, Ce block lumpiness be respectively less than 20mm.
8. a kind of preparation method of copper refining agent according to claim 5；It is characterized in that the Cu-Sr intermediate alloy is
It is prepared by following step:
Step I
Cathode copper by purity more than or equal to 99.995% is placed in the dry pot of graphite of vacuum melting furnace, is evacuated to 10-3After Pa
It is initially powered up melting, is vacuumized in heating, until cathode copper melts, obtains copper liquid；
Step II
Stopping vacuumizes, and is passed through the high purity inert gas that purity is more than or equal to 99.999%, and control furnace pressure is 0.5~1
Atmospheric pressure reduces melt temperature to 1150~1200 DEG C, D is added in copper liquid, is obtained
Cu-Sr intermediate alloy；The D is the Sr block that surface is coated with copper foil.
9. a kind of application of the copper refining agent as described in claim 1-4 any one；It is characterized by comprising by the refining agent
Oxygen-free copper is refined for waste and old copper magnet wire.
10. a kind of application of copper refining agent according to claim 9, it is characterised in that: be used for the refining agent waste and old
The technique that copper magnet wire produces oxygen-free copper bar by initial refining.
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| CN110527860B (en) * | 2019-09-23 | 2021-09-07 | 四川博鑫铜业有限公司 | Waste purple impure copper refining agent and preparation method and application thereof |
| CN111218561B (en) * | 2019-11-11 | 2021-11-12 | 宁波长振铜业有限公司 | Composite refining agent for reducing impurity element aluminum in waste brass and use method thereof |
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